CN1330296A - Moulding product - Google Patents

Abstract

A molded part obtainable by mixing a crystalline resin having at least one of a hydroxyl group, a carboxyl group and an ester linkage, an amorphous resin having at least one of a hydroxyl group, a carboxyl group and an ester linkage, and a polymerization catalyst while heating to prepare a resin composition and molding the resin composition.

Description

Mechanograph

The present invention relates to the mechanograph of a kind of machinery and electric property excellence, these goods are particularly suited for as the endless belt.

The endless belt is widely used in the imaging device (for example OA equipment), as photoreceptor band, intermediate transport band, conveying belt, transmission separating belt, charging valve, developing sleeve, photographic fixing band, toner travelling belt etc.

For example, the intermediate transport system comprises the intermediate transport member, forms toner image thereon and transfers to recording medium, gets on as paper.The endless belt is used as the intermediate transport member, makes its lip-deep toner charged and remove static.The resistance of used endless belt is set according to the pattern of system.The delivery transfer system comprises the delivery transmission member, fixed thereon of paper.After transferring on the paper that is fixed on the delivery transmission member from photoreceptor at toner, make paper separate from the delivery transmission member by removing static.In this used endless belt is to make the paper tape electricity and remove static as the surface that delivers transmission member.The resistance that is used to deliver the endless belt of transfer system also is to be provided with according to separately pattern.

The conducting loop-shaped band that is used for Xerox etc. to drive with high-tension for a long time by two or more rollers, therefore need have enough permanance.Locate being applied to intermediate transport system etc.,, transfer to then on the paper, make the distortion that can cause image with sagging or elongation in the operation because in a single day toner image is formed at and is with.In addition, the band that is used for the intermediate transport system need have electric conductivity to a certain degree, to carry out the transfer of electrostatic toner.

Along with the increase of nearest printer operating speed, the actuating speed of band has also increased, and this just further requires to improve the permanance of band.Transmit or used the bringing of intermediate transport system for the concatenation type delivery that four photoreceptors and toner spraying system are arranged, especially require its permanance and prevent that image fault, the place that this system attractive people notes from being its flying print ability.

As described below, the multiple moulding material that is used to produce above-mentioned endless belt has their shortcomings separately.

The endless belt of being made by rubber is easy to very much owing to their low elastic modulus stretch, and has bad toner fissility.Once attempted rubber and other material lamination, this makes complex manufacturing and increased cost.

The endless belt of being made by polycarbonate (below abbreviate PC as) has bad anti-crawl agentdefiection performance, and is easy to produce the crack when driving on roller.

Though the annular of being made by polyimide has excellent anti-crawl agentdefiection performance, because polyimide is a thermoset resin, not only be difficult to produce with continuously moulding, but also very expensive.In addition, their elastic modulus has applied load for the motor of rotating band up to 6000MPa.Except reducing tape thickness, can't reduce this load, in case but because dust enters between roller and the band, and perhaps band is scratched owing to rubbing with photoreceptor, the band that thickness reduces will be easy to produce the crack, will cause reliability bad like this.

It is good that the endless belt of being made by polyalkylene terephthalates (below abbreviate PAT as) is with than PC on the anti-crawl agentdefiection performance, but need improved thing also a lot.

Though the endless belt anti-crawl agentdefiection excellent performance that fluororesin is made, because its low Young modulus of about 1000 to 1400MPa easily stretches under tension force.The result is that color printing damages because of shearing force, perhaps is transferred to the toner distortion on the paper.

Can also use by PC and PAT, for example the polyblend of the polybutylene terephthalate endless belt (referring to JP-A-4-313757 and JP-A-6-149083) of making.Be with them to improve the anti-crawl agentdefiection performance with respect to PC, but still not enough.In addition, if use the PAT resin of degree of depth crystallization, will produce adverse influence to the dimensional accuracy of endless belt with higher proportion.

Conductive filler often joins as carbon black and to prepare the conducting loop-shaped band in the moulding resin.Yet the filler of adding will reduce mechanical property.

Though designed multiple endless belt up to now and be used for above-mentioned situation in practice, find to have gratifying mechanical property yet, for example anti-crawl agentdefiection performance and Young modulus, electric property are as the resistance and the endless belt of economy again.

Multiple thermoplastic resin is used in the structure or functional part of OA equipment, the structure member of the outside of for example aforesaid endless belt, automobile and internal part, apparatus etc.The thermoplastic resin that is used for these application need have high elastic modulus, excellent anti-crawl agentdefiection performance, excellent chemical resistance, dimensional accuracy and use required transparency for some.Thermoplastic resin is rough be divided into crystallization with unbodied.Usually, crystalline thermoplastic resin is excellence aspect anti-crawl agentdefiection performance and chemical-resistance, but bad aspect dimensional stability because of their high mold shrinkage coefficient, and does not have the transparency.On the other hand, the amorphous thermoplastic resin is excellent and transparent aspect the molding dimensional stability, but but not good aspect chemical-resistance.

To all requirements of stiffness energy, chemical-resistance and dimensional stability, crystalline thermoplastic resin and amorphous thermoplastic resin's polyblend is studied, when meeting molding to improve these performances.For example, in thermoplastic ester resin field, existing crystalline ester resin and the amorphous ester resin of reporting can come fine dispersion each other by quickening transesterification (interpolymerization).Yet owing to this technology of following reason does not also drop in the practical application.At first, acceleration transesterification (interpolymerization) prepares lower-molecular-weight component by depolymerisation to be finished, and produces foam when this causes molding.Secondly, cut off strand and will cause that molecular weight reduces, this will cause weaken (for example breaking elongation reduction) of moulded work mechanical property.Studied the method for transesterification of eliminating, but also succeedd aspect the mechanograph that provides a kind of elastic property (high elastic modulus) that had both had excellence also to have excellent anti-crawl agentdefiection performance to prevent that physical property from weakening.

The object of the present invention is to provide a kind of mechanograph, endless belt especially, it has high resiliency and excellent anti-crawl agentdefiection performance, chemical-resistance and molding dimensional stability, and does not produce physical deterioration because of reaction in the melting mixing process.

The thermoplastic resin polymer mixture by rough be divided into compatible with inconsistent.The incompatible polymers mixture presents island structure, because two kinds of thermoplastic resins do not mix fully by melting mixing.Under the widely different situation of two kinds of thermoplastic resin body integration numbers, the resin with larger volume mark is easy to form external phase (sea), and other the sort of resin is easy to form discontinuous phase (island).Under the very little situation of volume fraction difference, the difference of melt viscosity is influential for dispersed texture, and the less resin of melt viscosity is easy to form external phase and other the sort of resin is easy to form discontinuous phase.As if the interface must be arranged between the two in external phase and discontinuous phase, the incompatible polymer mixture is easy to destroy at the interface at this most, and this can reduce the anti-crawl agentdefiection performance.Therefore the inventor has expected waiting by graft copolymerization, block copolymerization and has strengthened this interface to improve the anti-crawl agentdefiection performance of mechanograph.

In addition, the compatible polymeric mixture does not have interface, promptly non-island structure usually between different resins.It is said the physical property of compatible polymeric mixture for example to be the mechanical property of representative with the anti-crawl agentdefiection performance, consistent with the blending ratio of two kinds of resins.Therefore, do not expect the polymer blended improvement that can obtain on the anti-crawl agentdefiection performance.The inventor recognizes if two kinds of materials are compatible and carry out copolymerization that mechanical property will be increased substantially as the anti-crawl agentdefiection performance each other.In other words, the copolymerized state that desired is in the thermoplastic polymer mixture no matter be compatible or inconsistent, can both improve mechanical property, as the elastic modulus and the anti-crawl agentdefiection performance of polyblend.

The inventor has had been noted that cheap thermoplastic resin-vibrin.People are known, and the molecule that the common experience of polyester is called transesterification when mixing cuts mutually and exchanges.Transesterification generally includes strand and cuts off, thereby causes foaming or becoming fragile, and causes the weakening of mechanical property.Yet, the inventor has expected that ester exchange reaction must take place simultaneously with the reaction of similar copolyreaction, and will be copolyreaction to ester exchange reaction guiding under the supposition specified conditions, eliminated simultaneously because the weakening of the mechanical property that the cutting of strand causes.On the basis of this assumption, the inventor has continued their research for composite material kind and composition, condition of moulding etc.

As a result of, disclosed the following fact.At first, polyester resin mixture can produce the polyblend that (1) has island structure, and (2) have the polyblend of island structure at copolymerization interface and the polyblend that (3) do not have island structure.The mechanical property that with the anti-crawl agentdefiection performance is representative increases progressively with the order of (1), (2) and (3).The adding of the 3rd component such as conductive filler seldom causes physical strength to reduce in (2) (island structure with copolymerization interface) or (3) (non-island structure).

Secondly, come under the situation of controlling resistance adding conductive filler for specific use, (2) (island structure with copolymerization interface) or (3) (non-island structure) has the filler that is fixed in the copolymer resins component, therefore present electrical stability, and the change of resistance can take place hardly in time.

The 3rd, (1) (island structure) and (2) (island structure with copolymerization interface) can be stretched in the wide temperature range hardly very much, and even at high temperature or experienced time of several days to several years and still keep high elastic modulus and creep-resistant property.

Based on these discoveries, the inventor is verified: by by heating time mixed crystallization resin, amorphous resin and the mechanograph that obtains of the moulding material for preparing of polymerization catalyst, with regard to physical properties such as stiffness, be better than these goods by any traditional handicraft preparation that comprises control methods such as ester exchange reaction, in addition, they have been found that at some condition counterdie goods and can have the transparency.

The invention provides a kind of mechanograph, wherein this mechanograph is the time will have crystalline resins at least a in hydroxyl, carboxyl and the ester bond by heating, have amorphous resin at least a in hydroxyl, carboxyl and the ester bond, and polymerization catalyst is mixed and is prepared that this resin combination of resin combination and molding obtains.

Accompanying drawing 1 is the mixing of polybutylene terephthalate and polycarbonate and the nuclear magnetic resoance spectrum of reacted product.

Accompanying drawing 2 is the zoomed-in view of accompanying drawing 1 part ii.

Accompanying drawing 3 is the side view of imaging device intermediate transport system, wherein: 1 ... photoreception rotating cylinder 2 ... charger 3 ... exposure light tool group 4 ... developing apparatus 5 ... descaler 6 ... conducting loop- shaped band 7,8,9 ... carrying roller

I] crystalline resins

Can be used in crystalline resins of the present invention and contain at least in hydroxyl, carboxyl and the ester bond a kind ofly, and have the crystallinity of common 10-100%.As long as satisfy these conditions, general resin can be used arbitrarily.

Preferred crystalline resins is PAT class (polyalkylene terephthalates), especially polybutylene terephthalate (below be called " PBT "), polyethylene terephthalate (PET) and PEN (PEN).PBT is more preferred because of its high percent crystallization in massecuite.Having higher percent crystallization in massecuite means under condition of moulding less to crystalline dependence.The crystallinity of PBT is stabilized in about 30% usually.As long as not serious infringement effect of the present invention is used for crystalline resins of the present invention and can comprises the copolymerization component.On its main chain ester bond is arranged, and the multipolymer of the ester bond that polymethylene glycol etc. introduces is arranged, can be used as the example of crystallization copolymer resins and be mentioned.

Though unqualified, the weight-average molecular weight of crystalline resins is about 10,000 to 100,000 usually.In this scope,, wish that as the demanding place of elongation at break its molecular weight is higher to mechanical property.In this case, crystalline resins preferably has 20,000 or higher weight-average molecular weight, preferred 25,000 or higher, and more preferably 30,000 or higher.[II] amorphous resin

Can be used in amorphous resin of the present invention and contain at least in hydroxyl, carboxyl and the ester bond a kind ofly, and do not have crystallization or crystallinity usually less than 10%.As long as satisfy these conditions, general resin can be used arbitrarily.

Suitable amorphous resin comprises polyester, the polymkeric substance of ester bond is for example arranged, as polymethylmethacrylate (PMMA) on PC and polyarylate (PAr) and the side chain.Polyesters is preferred, and wherein PC is especially preferred.As long as not serious infringement effect of the present invention is used for amorphous resin of the present invention and can comprises the copolymerization component.On its main chain that is adopted ester bond is arranged, and the multipolymer of the ester bond that polymethylene glycol and so on introduces is arranged, can be used as the example of amorphous copolymer resins and be mentioned.

Though unqualified, the weight-average molecular weight that is used for amorphous resin of the present invention is about 10,000 to 100,000 usually.In this scope, mechanical property such as the demanding place of elongation at break are wished that its molecular weight is higher.In this case, amorphous resin preferably has 20,000 or higher weight-average molecular weight, preferred 25,000 or higher, and more preferably 30,000 or higher.

Weight ratio with mixed crystalline resins and amorphous resin is not particularly limited, can have excellent chemical-resistance and anti-crawl agentdefiection performance usually with regard to crystalline resins, take in and arbitrary decision and have excellent size stability during the common molding of amorphous resin.The weight ratio of crystalline resins and amorphous resin is generally 1/99 to 99/1, is preferably 40/60 to 97/3, and more preferably 60/40 to 95/5, especially be preferably 70/30 to 90/10.Preferably use crystalline resins with the ratio higher than amorphous resin, because the dimensional stability when (i) amorphous resin of small scale is enough to improve molding and (ii) amorphous resin is excessive slightly will cause chemical-resistance, can obviously weaken as the performance of solvent in the coating resistant.

Preferably crystalline resins and amorphous resin do not have big difference on viscosity.If the difference on the viscosity is too big, any adjusting to preparation condition all can't obtain gratifying dispersed system.Specifically, the viscosity of crystalline resins and amorphous resin is preferably and makes the proportional range of its melt flow rate of measuring under the same conditions (below be called " MFR ") is 1/20 to 20/1, especially 1/10 to 10/1.MFR measures according to JIS K-7210.Measuring temperature needs to be close with the processing temperature of polyblend.For example, when using PBT and PC, their MFR measures down at 260 ℃, and this temperature is the processing temperature of PBT/PC polyblend, comes their viscosity of comparison thus.Measure the load that is applied and be generally 2.16kg.[III] polymerization catalyst

There is not special qualification to being used for polymerization catalyst of the present invention.Commonly used is the catalyzer that is used for polyesters.The catalyzer that preferably contains titanium is as alkyl titanate.Preferred alkyl titanate is titanium tetrabutoxide and four (2-ethylhexyl) ortho-titanate, and they can be available from as E.I.Du Pont, and its trade name is respectively TYZOR TBT and TYZOR TOT.

The polymerization catalyst of titaniferous preferably is used in combination with the compound of alkali metal containing, earth alkali metal or zinc, especially contains the compound of magnesium.Though without any qualification, the compound that contains magnesium preferably includes organic hydrochlorate, particularly magnesium acetate to it.

Polymerization catalyst is used in following amount: with the resin total amount, the tenor in the catalyzer is not less than 1ppm, preferred 10ppm or more, more preferably 20ppm or more.Because as known in the art, the ester resin is easy to depolymerization under the situation that plurality of heavy metal exists, and the upper limit of tenor is generally 10000ppm, preferred 1000ppm, more preferably 500ppm.If polymerization catalyst has too high activity, then this catalyzer has the trend that promotes depolymerisation.This causes molecular weight to reduce, thereby weakens the mechanical property of mechanograph.With the produced simultaneously foaming of lower-molecular-weight component also be problem.This do not wish the depolymerisation that takes place can be under suitable control condition of moulding or can with the metalchelated sequestrant of polymerization catalyst in the presence of suppressed.Used sequestrant comprises phosphite ester, phosphate, phosphate and hydrazine.They are easy to obtain from the market.For example, phosphite ester comprises the Irgaphos 168 that Chiba-Geigy (Japan) Ltd. provides, the PEPQ that PEP36 that Asahi Denka Kogyo K.K. provides and ClariantJapan K.K. provide; Hydrazine comprises the CDA-6 that IrganoxMD 1024 that Chiba-Geigy (Japan) Ltd. provides and Asahi Denka Kogyo K.K. provide.

If necessary, in total resin weight part, the sequestrant addition is 0.001 weight portion or more, preferred 0.01 weight portion or more.Should notice that excessive sequestrant is easy to reduce the activity of polymerization catalyst, causes can't obtaining to have the mechanograph of satisfactory physical property.From this viewpoint, the upper limit of sequestrant is generally 10 weight portions, preferred 5 weight portions.

In the preferred embodiment of using sequestrant, polymerization catalyst adopts big consumption in the above-mentioned preferable range, for example 50 arrive 500ppm, sequestrant also adopts big consumption in the above-mentioned scope, 0.1 to 3 weight portion for example, preferred 0.3 to 1 weight portion, condition of moulding (temperature, the residence time etc.) reaches the best.In this case, when suppressing depolymerisation, quickened the formation of the chemical bond between crystalline resins and the amorphous resin and the increase of molecular weight, prepared mechanograph thus with the superior physical properties that can't obtain so far.[IV] other component

If necessary, as long as effect of the present invention is not had grievous injury, mechanograph of the present invention can comprise other component, for example other thermoplastic resin, elasticity thermoset resin, filler and other adjuvant.

The thermoplastic resin that can be used in combination comprises polypropylene; High density, middle density, low-density or linear low density polyethylene (LLDPE); Propylene-ethylene block or random copolymers; Rubber or latex component, ethylene-propylene copolymer rubber for example, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer or their hydrogenated derivatives, polybutadiene and polyisobutylene; Polyamide, polyamide-imides, polyacetal, polyarylate, polycarbonate, polyimide, liquid crystal polyester, polysulfones, polyphenylene sulfide, poly-bisamide triazole, polyethers-acid imide, polyetheretherketone, acryl resin, polyvinylidene fluoride, polyvinyl fluoride, the polychlorostyrene ethylene trifluoride, ethene-tetrafluoroethylene multipolymer, hexafluoro-propene-TFE copolymer, tetrafluoroethene-perfluoroalkyl vinyl ether multipolymer, alkyl acrylate copolymer, polyester-ester copolymer, polyether ester multipolymer, polyether-amide multipolymer, polyurethane copolymer, and their potpourri.

Thermoset resin comprises epoxy resin, melamine resin, phenolics, unsaturated polyester resin and composition thereof.

Filler comprises lime carbonate (coarse whiting and fine particle calcium carbonate), talcum, mica, silica, alumina, aluminium hydroxide, zeolite, wollastonite, zeyssatite, glass fibre, glass microballoon, bentonitic clay, asbestos, hollow glass microbead, graphite, molybdenum disulfide, titania, carbon fiber, aluminum fiber, styrene tempering fiber, brass fiber, aluminium powder, wood powder, rice husk, metal powder, conducting metal oxide, organometallics and organic metal salt.

Can add the mechanograph that carbon black makes the present invention be used as seamless band etc. and obtain electric conductivity.The example of carbon black comprises channel black, furnace black and acetylene black etc.Handle with coupling agent on the surface of used carbon black, to improve its dispersive property.The example of coupling agent comprises silane coupling agent, aluminate coupling agent, titanate coupling agent and zirconate coupling agent etc.Can use the carbon black of single kind or be used in combination multiple carbon black.In total composition, the addition of carbon black is generally 3 to 30% weight, preferred 10-20% weight.

Other adjuvant that can add this mechanograph comprises antioxidant (for example Irgaphos 168, Irganox 1010 and Phosphorus antioxidant), thermal stabilizer, plastifier, light stabilizer, ultraviolet light absorber, neutralizing agent, lubricant, antifoggant, anticaking agent, the sliding formwork agent, crosslinking chemical, crosslinking coagent, colorant, fire retardant and spreading agent.[V] heat is mediated and molding

Mediate crystalline resins, amorphous resin and polymerization catalyst in the time of heating and prepare the resin combination of fusion.Directly this molten resin composition of molding obtains mechanograph of the present invention, perhaps forms moulding mixture (for example pellet), molding then earlier.Also can mediate crystalline resins, amorphous resin and polymerization catalyst are made masterbatch earlier, be mixed with moulding material with other resin combination then by heat.Select hot kneading condition to make it in kneading process, to form key between the crystalline resins and amorphous resin, be used to prepare resin combination, or be used for molding.Under any situation, heating-up temperature wants enough high for the potpourri that is melted, otherwise can't obtain sufficient dispersion.Specifically, with reference to the fusing point of crystalline resins, heating-up temperature preferably is equal to or higher than the fusing point of crystalline resins, and is more preferably high 10 ℃ or more than its fusing point.Yet it should be noted that too high heating-up temperature is easy to cause thermal decomposition, thereby cause physical deterioration.From this viewpoint, heating-up temperature preferably is not higher than fusing point+80 ℃ of crystalline resins, more preferably no higher than fusing point+60 of crystalline resins ℃.

Suggestion is carried out drying with mixed raw material before heat is mediated, the mechanograph of gained is tending towards possessing the better physical performance like this.Under certain some situation, can heat mediating the resin combination that obtains at its fusing point or the temperature that is lower than its fusing point, before molding, to form ester bond by heat.

Polymerization catalyst has promoted the reaction between crystalline resins and the amorphous resin, has the mechanograph of superior physical properties with preparation.Because heat is mediated temperature and heat time heating time is bigger for the influence of the reaction that is promoted, so should determine hot kneading condition in the dispersed of monitoring gained mechanograph.If produce the lower-molecular-weight component accessory substance in the reaction, and from system, do not remove, just will cause molecular weight reduce with mechanograph in foam.Moment before foaming has one to seem optimal reactiveness.Therefore, in order to obtain optimized hot kneading condition, for example should be set to the residence time slightly be shorter than the time that foam takes place, this can be decided by experience.

There is no particular limitation to means that heat is mediated, and any technique known all is suitable for.For example, being used for earlier, the kneader of preparation resin combination (moulding mixture) comprises single screw extrusion machine, double screw extrusion machine, Banbury mixer, roller, Bradley Bender plastometer and mediates mixer.But the means cause moulding mixture of application of known obtains mechanograph, for example injector and extruder.[VI] analyzes

The analytical approach of mechanograph of the present invention is described below, but is not limited to this.Usually, mechanograph is dissolved in the solvent, then filters to remove inorganic filler.Solvent for use comprises chloroform, methylene chloride and hexafluoroisopropanol.Can directly analyze the resin Composition that has dissolved, perhaps, if necessary, before analysis, separate and purify with liquid chromatography or gel permeation chromatography (GPC).Resin Composition through purifying is applicable to that measuring resin forms (for example PC, PET etc.), determines in conjunction with residue, uses common means, assesses crystallinity as the instrumental method of nuclear magnetic resonance and so on.In addition, the kind of polymerization catalyst and content can wait easily by above-mentioned resin solution ICP-AES and measures in the mechanograph.(chemical bond between crystalline resins strand and the amorphous resin strand)

According to the present invention, in the presence of polymerization catalyst, between the strand of crystalline resins and amorphous resin strand, react to form therebetween chemical bond.The result is the affinity each other that has improved two kinds of resins, and with this mixed system of immediate mode fine dispersion, obtain thus to have crystalline resins intrinsic anti-crawl agentdefiection performance and amorphous resin the mechanograph of intrinsic dimensional stability (also having the transparency under certain conditions).

The ratio that exists for this chemical bond does not limit especially, in principle should be high as far as possible.Particularly preferably be, the chemical bond between every mole of crystalline resins strand and the amorphous resin strand, the total amount of corresponding crystalline resins and amorphous resin is 1,000,000g or still less, especially 300,000g or still less, particularly 100,000g or still less.

The amount of chemical bond can wait by NMR (Nuclear Magnetic Resonance) analysis and measure.To provide an example of measuring with nuclear magnetic resonance method below, wherein PBT is as crystalline resins, and PC is as amorphous resin.

Instrument: JEOL GSX400

Solvent: 1,1,1,2,2,2-hexafluoroisopropanol/d-chloroform=3/7 (volume ratio)

Integral number of times: 128

Interior mark: TMS

Provided the nuclear magnetic resoance spectrum with this assay in attached Fig. 1 and 2, accompanying drawing 2 is the enlarged drawing of part II in the accompanying drawing 1.

When the carboxyl of terephthalic acid (TPA) was attached to butylene glycol and be attached to bisphenol-A (below be called " BPA "), the hydrogen atom on its terephthalic acid (TPA) (below be called " TPA ") phenyl ring can demonstrate different chemical shifts.Shown in following molecular formula, four hydrogen atom (H on the TPA phenyl ring of PBT molecule ^d) be equal to each other usually, and show unimodal at chemical shift 8.07 places.

On the other hand, the hydrogen atom that is attached on the TPA phenyl ring among the PBT on the BPA of PC has different chemical shifts, as shown in following molecular formula:

TPA (from PC) among TPA (from PBT)-BPA

Be hydrogen atom H ^bAnd H ^cPresent bimodal at 8.25 and 8.13 places respectively.

(d) be the ratio of (TPA in the PBT molecule) and (being attached to the TPA on the PC) with the peak area ratio of [(b)+(c)].In the special case shown in attached Fig. 1 and 2, (d): [(b)+(c)] area is than=100: (0.4654+0.5635) ≈ is 99.01: 0.99, and per 100 moles of PBT structural units contain TPA (from PBT)-BPA (from PC) key of 0.99 mole in the expression resin combination.Because clearly this resin combination contains butylene glycol (from PBT)-carbon (from the PC) key of same amount, is appreciated that every 100mol PBT structural unit has the PBT-PC key of 1.98mol.

(butylene glycol+TPA), the content of PBT-PC key is per 22000 (220 * 100mol) g PBT 1.98mol to PBT structural unit with 220 structural unit molecular weight as follows.

The PBT structural unit

Structural unit molecular weight: 220/ every unit

Therefore, the PBT quality of every mole of PBT-PC key is about 11000 (22000/1.98).In this example, the PBT/PC weight ratio is 7/3, and the resin content of every mole of PBT-PC key (PBT quality+PC quality) is 16000g (11000/0.7).(molecular weight)

The improved physical property of mechanograph of the present invention is believed the chemical bond of giving the credit between crystalline resins strand and the amorphous resin strand, in the presence of polymerization catalyst, mediate these resins and form this chemical bond, keep or increase the molecular weight of resin combination simultaneously on the whole by heat.Therefore preferred resin combination has high as far as possible molecular weight.The true molecular weight of measuring multipolymer of the present invention is difficult.Therefore the weight-average molecular weight of every kind of resin is measured by GPC under the same conditions in the present invention, and handles by the polystyrene conversion.With the value calculated thus (below be called " polystyrene conversion weight-average molecular weight ") as general-purpose indexes.Be about to the 20mg sample dissolution to 0.5 ml 1,1,1,3,3, spend the night in the mixed solvent of 3-hexafluoro-2-propyl alcohol and 0.2ml chloroform, and to the solvent that wherein adds 25ml as moving phase.Filter this solution by 0.22 μ m filtrator, be used for the sample solution that SEC measures with preparation.Finish this measurement from adding in 12 hours that moving phase begins.

The SEC measuring condition:

Solvent: chloroform/acetate=99.5/0.5 (volume ratio)

Flow velocity: 1.0ml/min

Elution volume: 0.02ml

Post: two AD806M/S posts (Showa Denko KK. provides)

Column temperature: 30 ℃

Detecting device: UV 254nm

Analyze 12 molecular weight from 500 (A-500) to 2,890, single decentralized standard polystyrene sample (Tosoh Corp. provides) that 000 (F0288) changes, with the preparation calibration curve, the PS that therefrom calculates sample transforms molecular weight.

Usually represent that with formula (1) PS of the resin combination that crystalline resins, amorphous resin and the kneading of polymerization catalyst heat obtain afterwards transforms weight-average molecular weight and (is called Mw ₃):

Mw ₃〉=[X/ (X+Y)] * Mw ₁+ [Y/ (X+Y)] * Mw ₂Wherein X is the charge ratio (weight portion) of crystalline resins; Mw ₁PS conversion weight-average molecular weight for crystalline resins; Y is the charge ratio (weight portion) of amorphous resin; Mw ₂PS conversion weight-average molecular weight for amorphous resin.

Mw ₃Preferably use formula (2) to represent:

Mw ₃〉={ [X/ (X+Y)] * Mw ₁+ [Y/ (X+Y)] * Mw ₂} * 1.1 more preferably use formula (3) to represent:

Mw ₃≥{[X/(X＋Y)]×Mw ₁＋[Y/(X＋Y)]×Mw ₂}×1.2

As the result of heat mixing, importantly Mw ₃Than Mw ₁And Mw ₂Arithmetic mean big.Even by high molecular weight resin (Mw ₁And Mw ₂) resin combination that obtains has high molecular (Mw ₃) situation under, if Mw ₃Less than Mw ₁And Mw ₂Arithmetic mean, if promptly in hot mixed process molecular weight reduce, the mechanograph of gained can not obtain gratifying physical property.Though from this viewpoint for Mw ₃Absolute value there is no particular limitation, but as a whole need higher molecular weight.Mw ₃Be generally 130,000 or higher, preferred 140,000 or higher, preferred especially 150,000 or higher.

Measure as can be known according to said method, it is such that true weight-average molecular weight and PS transform weight-average molecular weight mutual relationship between the two, for example, weight-average molecular weight is that 40,000 PBT and weight-average molecular weight are that 28,000 PC has 122 respectively, 000 and 64,000 PS transforms weight-average molecular weight.

(the analysis of carrying out with DSC) to melting peak

With compare with the mechanograph that comprises common technology preparation such as control ester exchange reaction etc., mechanograph of the present invention is excellent on physical property, for example dimensional stability and the anti-crawl agentdefiection performance during molding.The advantage of this mechanograph aspect the thermal history characteristic can be analyzed by the thermal behavior in the differential scanning calorimetry (DSC).The analysis of thermal behavior has been shown the motion of superpolymer under heating from the microcosmic chain movement to macroscopic motion.For example, under glass transition temperature, observe micro-Brownian movement, find folding movement at the fusing point place.

Mechanograph of the present invention has shown this thermal behavior in DSC, difference shown in the melting peak that heats up for the second time after the gentle cooling in peak shown in the feasible melting peak that heats up for the first time between the peak temperature is 30 ℃ or littler, preferred 20 ℃ or littler, especially preferred 10 ℃ or littler.These peaks provide whether mechanograph is in time dependent state, and in other words, whether mechanograph contains residual non-reacted parts.It seems that difference means that greatly mechanograph will have big variation at aspects such as size, mechanical propertys in time between these peaks.

The difference of the gentle melting peak temperature that heats up for the second time of the melting peak that heats up for the first time greater than 30 ℃ situation under, mechanograph at high temperature its tensile modulus can reduce significantly, this is because have the cause of a large amount of unreacted resins.In this case, the endless belt is easy to stretch, and perhaps at high temperature or in several days to several years the use is out of shape because of creep.Temperature contrast less than 30 ℃ situation under, the minimizing of tensile modulus has been suppressed under the high temperature, creep obviously reduces.Yet, have gratifying normal temperature mechanical property, for example durability and tensile modulus, but the mechanograph that can deform in time can't be used as precision element.Therefore, importantly the difference of above-mentioned melting peak should be in specific scope.(dispersed)

People know, even common two kinds of thermoplastic resins can not mix fully yet under molten condition and when presenting fluidic structures, in the place that two kinds of resins have widely different volume fraction, the resin that allegedly has the larger volume mark is easy to form external phase (sea), and another resin is easy to form discontinuous phase (island).Under the little situation of volume fraction difference, the differentia influence of melt viscosity is to island structure, and the resin with less melt viscosity trends towards forming external phase, and another resin is tending towards forming discontinuous phase.

Mechanograph of the present invention is the polyblend with island structure.Polyblend, particularly those comprise that crystallographic component and amorphous component or those contain the polyblend of filler etc., the variation of experience structure in the cooling step after the hot melt step sometimes.For example, when resin compound is cooled off rapidly or in the presence of filler etc., the material that those should crystallization sometimes fully crystallization and in the mechanograph of gained part keep amorphous state.In this case, will restart crystallization, and cause significantly contraction or physical strength significantly to reduce when being in high temperature mechanograph of following time.

In order to prevent the generation of this situation, the crystallizable component outside the alloying material should present crystalline state in mechanograph.Though the polyblend that obtains by melting mixing commonly used can have the discrete particles size that is not less than 100nm, the fine dispersion resin becomes possibility to several nanometers or littler particle size under the condition of suitably selecting but the invention enables, and obtains almost transparent mechanograph thus.Though unqualified, can use transmission electron microscope, observe disperse state by check with the ultra-thin section of the sample of ruthenium tetroxide dyeing.(thermal treatment)

If necessary, can heat-treat, with the further physical property of improving the gained mechanograph.According to material resin, under 60-200 ℃, preferred 70-120 ℃, carried out preferred thermal treatment in 10-30 minute 5-60 minute usually.Thermal treatment is especially effective for endless belt etc., and the improvement of flex life and tensile modulus is described below.The application of [VII] mechanograph

The structure or the functional part that comprise (but being not limited to) OA equipment of mechanograph of the present invention with being widely used, the structure member of automobile external or internal part, apparatus, general film etc.Particularly they are used in the OA equipment, and specifically as functional part, these parts are very strict for the requirement of dimensional accuracy, anti-crawl agentdefiection performance, elongation at break etc.For example, endless belt of the present invention shows excellent performance, rarely defective simultaneously for example be full of cracks seldom occurs and extends disadvantage when as the intermediate transport band in imaging device such as Xerox, laser printer and the facsimile recorder, conveying belt, photoreceptor band etc.(endless belt)

As the endless belt of a successful Application of mechanograph of the present invention, preferably by in double screw extrusion machine etc. crystalline resins, amorphous resin and polymerization catalyst being mixed and granulation, and molded this pellet obtains.

Molding methods comprise (but being not limited to) continuously melt extrude injection moulding, blowing and trapped-air process etc.Melt is extruded the most continuously.Especially preferred extrusion molding downwards guarantees the interior cold axle system and the Vacuum shaping system of accurate control tube internal diameter.In cold axle system be highly preferred.The temperature in the molding and the residence time should be adjusted to each prescription and conform to, to obtain mechanograph with satisfactory physical property.With the method production endless belt, promptly the seamless band is especially preferred embodiment.(physical property of endless belt)

Gained of the present invention endless belt has following physical property.

(1) thickness

If the carry roller of operation endless belt has small curve, too thick endless belt is easy to fracture owing to distortion difference is big between its outside surface and the inside surface, and causes toner distortion or the diffusion of transferring to its outside, causes image fault.In addition, owing to entering the micronic dust between roller and the band or contacting the scratch that produces, make too thin endless belt also be easy to take place crack and fracture with photoreceptor etc.Therefore, endless belt of the present invention has the thickness of 50-1000 μ m usually, preferred 70-300 μ m, more preferably 100-200 μ m.

(2) anti-crawl agentdefiection performance

When the endless belt was used for imaging device as intermediate transport band etc., it should have gratifying anti-crawl agentdefiection performance.Otherwise can produce the crack, cause the imaging failure.The anti-crawl agentdefiection performance can come quantitative Analysis to come out according to the number of flexings that JIS P-8115 (measuring folding permanance with the MIT verifier) (below be sometimes referred to as flex life) measures.Need the endless belt that more repeatedly deflection just can be ruptured to be not easy to fracture, have anti-crawl agentdefiection performance preferably.In order to guarantee the function as the endless belt, deflection to the number of times of fracture is generally 500 or more.Preferred deflection to the number of times of fracture is 5000 or more, when special 10,000 or more.Have 30,000 or more deflections to the endless belt of breaks can not rupture basically.

(3) tensile modulus

The endless belt preferably has high tensile modulus.When being used for imaging device, during as intermediate transport band etc., the endless belt with low tensile modulus can slightly stretch, and this will cause defective, produce as the color shear.Preferred tensile modulus is 1500MPa or higher, especially 2, and 000MPa or higher.In order obviously to suppress defective such as color shear, the most preferred 2,500MPa or higher tensile modulus.It should be noted that the endless belt with too high tensile modulus not only forces at the engine excess load of rotating band, and be easy to cause fracture.From this viewpoint, the tensile modulus of endless belt is generally 5000MPa or lower, preferably 4500MPa or lower.

The temperature dependency of tensile modulus when normally 40 ℃ of following tensile moduluss are 5 ℃ tensile modulus 60% or higher, preferred 70% or higher, especially preferably 80% or higher, when 60 ℃ of following tensile moduluss are 5 ℃ 20% of tensile modulus or higher, preferred 40% or higher, especially preferably 60% or higher.In other words, preferably when temperature from 5 ℃ be increased to 40 (℃ the time tensile modulus slightly change, when temperature moderate reduction when 40 ℃ are increased to 60 ℃.If 40 (℃ following tensile modulus is less than 60% of 5 ℃ of tensile moduluss, and the band that is used for printer, duplicating machine etc. is easy to stretch under summer or hot conditions, causes image fault or creep.Importantly 60 ℃ of following tensile moduluss be generally 5 ℃ of following tensile moduluss 20% or more.If 60 ℃ of following tensile moduluss are less than 20% of 5 ℃ of tensile moduluss, this band is easy to because of through in a few days or the change in size that causes of the creep of using in several years.

In general, soft plastics are tending towards having long flex life but tensile modulus is low, and duroplasts is tending towards having high tensile modulus but is fragility, and flex life is short.An advantage of the present invention be mechanograph have kept simultaneously long flex life PBT or PC intrinsic high tensile modulus.

(4) elongation at break

In tension test, importantly the endless belt should have and is generally 30% or more, and preferred 50% or more, preferred especially 100% or more breaking extension rate.Usually, the elongation of mechanograph with higher elasticity modulus is lower, has less breaking elongation.Yet verified importantly endless belt should have suitable thickness, along having 30% or higher breaking elongation on circumference and the Width usually, has high elastic modulus again to reduce image fault and to avoid crack propagation to keep long durability.Breaking elongation can make crack propagation less than 30% endless belt, and does not have enough permanance, as serviceable life of 200,000 to 300,000 for imaging device.

(5) surface resistivity and specific insulation

As required, make that by adding the material that conductive filler maybe can improve conductivity endless belt of the present invention is conductive.According to application, it is 1 * 10 that the resistance of band can be set to surface resistivity ¹To 1 * 10 ¹⁶Ω, perhaps specific insulation is 1 * 10 ¹To 1 * 10 ¹⁶Ω cm.More particularly, the endless belt that is used as the photoreceptor band preferably has low-resistivity, and for example surface resistivity is 1 * 10 ¹To 1 * 10 ⁹Ω, perhaps specific insulation is 1 * 10 ¹To 1 * 10 ⁹Ω cm flees to inside surface to allow the electric charge on the outside surface.Endless belt as the intermediate transport band preferably has the resistivity that can promote electrostatic electrification and elimination, and for example surface resistivity is 1 * 10 ⁶To 1 * 10 ¹³Ω or specific insulation are 1 * 10 ⁶To 1 * 10 ¹³Ω cm.Endless belt as conveying belt preferably has the high resistivity that can guarantee chargeability and prevent to rupture under high voltage, and for example surface resistivity is 1 * 10 ¹⁰To 1 * 10 ¹⁶Ω or specific insulation are 1 * 10 ¹⁰To 1 * 10 ¹⁶Ω cm.

The surface resistivity of endless belt distributes best narrower.Specifically, the index difference between the minimum and maximum surface resistivity in single endless belt is preferably 2 or littler, and maximal value and minimum value all drop in the above-mentioned preferable range.The enough Hiresta or the Loresta that produces as Dia InstrumentsLtd. of surface resistivity energy of endless belt, or the R8340A that Advantest Corp. produces measures easily.

Describe the present invention now with reference to embodiment, but be understandable that the present invention is not limited to this.

In embodiment and comparative example, use material beneath (all umbers are weight portion) to forming shown in 3 according to table 1.

PBT (crystalline ester resin): weight-average molecular weight: 40,000; PS transforms weight-average molecular weight: 122,000

PC (amorphous ester resin): weight-average molecular weight: 28,000; PS transforms weight-average molecular weight: 64,000

Polymerization catalyst: titanium tetrabutoxide and magnesium acetate

Thermal stabilizer: the phosphorus type antioxidant PEPQ carbon black that Clariant Japan K.K. provides: the Denka Black that Denki Kagaku Kogyo K.K. provides (heat is mediated)

, under condition shown in 3, raw material is mediated and granulation at table 1 with double screw extrusion machine PMT32 (IKG KK. provides).(production of endless belt)

With the pellet drying, and being that the extruder of 40mm is extruded from diameter, is the pipe that the ring-like mouthful of mould of 180mm becomes fusion through diameter, cools off and takes off this pipe, and it is long with production conducting loop-shaped band to cut into 340mm.Condition of moulding is listed in the table.(evaluation)

The sample of appropriate size is cut in the gained endless belt, and estimates according to following method.

1) flex life (number of times of deflection)

Measure according to JIS P-8115.Under the 1.5kgf tension force that the MIT tester provides, with left and right be 135 ° angle of deflection, the sample of wide 15mm, long 100mm is carried out deflection with 175 times/minute, measure the number of times of deflection when rupturing.

2) surface resistivity (Ω)

Select ohmer for use according to resistivity level.

For those resistivity is 1 to 1 * 10 ⁶The sample of Ω, along the circumferential direction with the spacing of 20mm, the Row Rester that provides with Dia Instruments Ltd. measures its surface resistivity.

For those resistivity is 10 ⁶To 1 * 10 ¹³The sample of Ω, under the condition of 500V and 10 seconds, along the circumferential direction with the spacing of 20mm, the Hiresta (HA terminal) that provides with Dia Instruments Ltd. measures its surface resistivity.

For those resistivity is 10 ¹³To 1 * 10 ¹⁶The sample of Ω, under the condition of 500V and 10 seconds, along the circumferential direction with the spacing of 100mm, the ultra-high resistance meter R8340A (JIS electrode) that provides with Advantest Corp. measures its surface resistivity.

For this assessment, application be 10 seconds values.

3) specific insulation (Ω cm)

Under the condition of 100V and 10 seconds, along the circumferential direction with the spacing of 20mm, the HirestaHRS Probe that provides with DiaInstruments Ltd. measures its specific insulation.

4) differential scanning calorimetry (DSC)

Under the heating rate of 10 ℃/min, the SSC-5200 that provides with Seiko Electronic Componets Ltd. finishes differential scanning calorimetry.Sample is heated to 300 ℃ carries out the dsc measurement first time, the speed with 10 ℃/min is cooled to room temperature afterwards.Under same condition, heat this sample once more, to finish dsc measurement for the second time.The melting peak temperature of DSC curve for the first time and poor between the melting peak temperature of DSC curve have for the second time been obtained.

5) thickness

Along the circumferential direction with spacing, the usefulness Tokyo Seimitsu Co. of 20mm, the micrometer that Ltd. produces comes the thickness of measure annular band.

6) Dai permanance

The endless belt is installed in the imaging device as the intermediate transport member, and carries out imaging operation continuously.Estimate the permanance of band according to the quantity of output copy till rupturing.

Accompanying drawing 3 is for being used for the intermediate transport system side view outline with the endurancing imaging device.Around photosensitive drums (photoreceptor) 1, arranging the electronic imaging unit, promptly charger 2, as the optical system 3 of the exposure usefulness such as semiconductor laser of light source, contain the developing element 4 of toner and from the descaler 5 of photoreceptor 1 removing remaining toner.Conducting loop-shaped band 6 is installed on carry roller 7,8 and 9, with the operation of the direction shown in the arrow, and synchronous with the sense of rotation of the photoreceptor 1 shown in the arrow.This system of usefulness as described below carries out imaging.With 2 pairs of chargers surperficial uniform charging with the photoreceptor 1 of the rotation of direction shown in the arrow A, read in the signal that (not shown) such as unit sends then according to image, carry out imaging with the light source of optical system 3 and expose, on photoreceptor 1, to form electrostatic latent image.Is toner image with developing cell 4 with image development, and this image comes static to be sent on the endless belt 6 by static delivery unit 10, transfers to then on the copy paper 11, and wherein this copy paper passes through between carry roller 9 and carrying roller 12.

Embodiment 1

Dry in advance PBT, PC, titanium tetrabutoxide under about 130 ℃, magnesium acetate and PEPQ (thermal stabilizer) and heating kneading in double screw extrusion machine prepare pellet with this.Resin temperature and hold-up time in the control double screw extrusion machine are to suppress the reaction in this stage.The application diameter is that the ring-like mouthful of mould of 180mm melt extrudes this pellet, controls extrusion capacity and draws speed, and be the film of 140 μ m to form thickness.In the film extrusion, control the temperature of resin and hold-up time simultaneously so that reaction can be carried out with suitable degree in extruder, to obtain transparent membrane.In table 1, listed dispersed texture, PS transforms weight-average molecular weight (Mw), the outward appearance of the machinery and the extrusion film of electric property and gained.When film 80 ℃ of following thermal treatments in the time of 10 minutes, tensile modulus increases by 5%.

Comparative example 1

Except not using the polymerization catalyst, obtain extrusion film with the method identical with embodiment 1.In order to get rid of the influence of the metal ingredient that exists among the PBT, PBT is dissolved in the solvent, filters in post and re-uses except that after desolvating.What be different from embodiment 1 is not obtain transparent membrane, has regulated condition of moulding (molding temperature and hold-up time).Dispersed texture, characteristic and gained appearance of films in table 1, have been listed.

Table 1

			Embodiment 1	Comparative example 1
					Form	PBT		70 parts	70 parts
PC		30 parts	30 parts
				Catalyzer (in total resin weight)		The content of titanium	60ppm
The content of magnesium	25ppm
			PEPQ			0.3 part	0.3 part
The kneading condition	Design temperature							230℃	230℃
			Driving screw speed		150rpm	150rpm
	Output						15kg/hr	15kg/hr
			Hold-up time		About 2min	About 2min
	Condition of moulding	Molding temperature					260℃	260℃
Hold-up time				6min	6min
		Thickness				140μm±14μm	140μm±14μm
The physical property of band	Dispersed texture				Form			Fabric of island-in-sea type (fine dispersion)	Fabric of island-in-sea type
		The discrete particles size	≤1nm	About 100nm
					PC transforms Mw		150,000
	Mechanical property	Flex life	90,000	5,000
					Tensile modulus	2200MPa	2300MPa
		Breaking elongation	340％	90％
					Surface resistivity	Maximum		5×10 15 Ω	5×10 15 Ω
	Minimum
			2×10 15Ω	1×10 15Ω
	Outward appearance				Transparent	White (opaque)

Embodiment 2

Dry in advance PBT, PC, titanium tetrabutoxide, magnesium acetate, PEPQ and carbon black, and mediate simultaneously in heating and to prepare pellet.Using diameter and be the ring-like mouthful of mould of 180mm and interior cold axle continuous fusion that external diameter is 170mm and extrude this pellet, control extrusion capacity simultaneously and draw speed, is the seamless endless belt of 169mm to form internal diameter.As shown in table 2, the mechanical property excellence of gained film has 58,000 flex life and high tensile modulus.When this band is used as the intermediate transport band of imaging device as shown in Figure 3, can obtain gratifying image.Still there is not the crack to produce even in continuous imaging, obtain after 100,000 parts of copies.

Can be by the mechanograph that hold-up time and molding temperature obtain to have satisfactory physical property suitably be set in the kneading process of molding.When with this endless belt 80 ℃ of following thermal treatments in the time of 20 minutes, tensile modulus increases by 8%.

Embodiment 3

Hold-up time, applicating adn implementing example 2 identical methods obtain the endless belt when changing the PBT/PC weight ratio and increasing molding.As shown in table 2, the gained band also presents gratifying physical property in this case.Because the ratio of PBT/PC changes the optimum reaction condition that makes system and changes, so be necessary when molding, to prolong the hold-up time.When with the endless belt 80 ℃ of following thermal treatments in the time of 10 minutes, tensile modulus increases by 5%.

Embodiment 4

Except reducing content of carbon black, the identical process that repeats embodiment 2 obtains the endless belt that surface resistivity improves.As shown in table 2, mechanograph presents dispersed system and the gratifying physical property similar to embodiment 2.When this band is used as the conveying belt of imaging device, can obtain gratifying image.

Embodiment 5

Except increasing content of carbon black, the identical process that repeats embodiment 2 obtains the endless belt that surface resistivity reduces.As shown in table 2, mechanograph has also presented uniform dispersed system and gratifying physical property.When this band is used as the photoreceptor band that has the photoreception layer on it in imaging device, can obtain gratifying image.When with the endless belt 80 ℃ of following thermal treatments in the time of 10 minutes, tensile modulus increases by 7%.

Comparative example 2

Except not using the polymerization catalyst, applicating adn implementing example 2 identical methods obtain the endless belt.In order to get rid of the influence of the metal ingredient that exists among the PBT, PBT is dissolved in the solvent, filters in post and re-uses except that after desolvating.Identical on tensile modulus among gained band and the embodiment 2, but flex life is relatively poor.Microscopic is shown as island structure, and wherein PC forms the island.When the gained band is used as the intermediate transport band of imaging device, can obtains gratifying image, but after printing 8000 copies continuously, can produce the crack.

Table 2

			Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example 2
								Form	PBT (weight portion)		60	77	?60	60	?60
PC (weight portion)		26	9	?26	26	?26
							Catalyzer (ppm is in total resin weight)		The content of titanium	60	60	?60	60
The content of magnesium	25	25	?25	25
						Carbon black (weight portion)			14	14	?11	17	?14
PEPQ (weight portion)		0.3	0.3	?0.3	0.3									?0.3
						The kneading condition	Be provided with temperature (℃)		230	230	?230	230	?250
Driving screw speed (rpm)		150	150	?150	150									?150
							Output (kg/hr)		15	15	?15	15	?40
Hold-up time (min)		About 2	About 2	About 2	About 2									About 2
							Condition of moulding	Molding temperature (℃)		260	260	?260	260		?260
Hold-up time (min)		12	20	?11	14	?12
								Thickness (μ m)			140±14	140±14	?140±14	140±14	?140±14
The physical property of band	Dispersed texture	Form	Non-island structure	Non-island structure	Non-island structure	Non-island structure	Island structure
								The discrete particles size	*	*	?*	*	About 100
		PC transforms Mw		25,100										?99,900
	Mechanical property							Flex life	58,000	51,000	?70,000	32,000	?3,000
		Tensile modulus (MPa)	2600	2600	?2500	2700	?2700
								Breaking elongation (%)	340	360	?360	280	?80
		Surface resistivity (Ω)	Maximum	5.0×10 10	4.0×10 10	?8.2?×10 12	7.0×10 5							?4.0?×10 10
	Minimum							9.0×10 9	8.0×10 9	?1.0×10 12	3.0×10 5	?1.0×10 10
			The permanance of band		There is not the crack to produce after producing 100,000 copies	There is not the crack to produce after producing 100,000 copies	There is not the crack to produce after producing 100,000 copies						There is not the crack to produce after producing 100,000 copies	Produce the crack after producing 8000 copies

^*There is not granule boundary clearly

Embodiment 6-12

Dry in advance PBT, PC, titanium tetrabutoxide under about 130 ℃, magnesium acetate and PEPQ, heating and kneading prepare pellet.Resin temperature and hold-up time during control is mediated are to suppress the reaction in this stage.Using diameter and be the ring-like mouthful of mould of 180mm and interior cold axle that external diameter is 170mm and come continuous fusion to extrude this pellet, control extrusion capacity simultaneously and draw speed, is the seamless endless belt of 169mm to form internal diameter.The extrusion molding condition that is provided with as shown in table 3 is so that reaction can be carried out suitable degree in extruder, to obtain the endless belt.Dispersed texture, machinery and electric property and the permanance of gained endless belt in table 3, have been listed.

Comparative example 3

Except not using the polymerization catalyst, obtain the endless belt with the method identical with embodiment 6.In order to get rid of the influence of the metal ingredient that exists among the PBT, PBT is dissolved in the solvent, filters in post and re-uses except that after desolvating.Dispersed texture, machinery and electric property and the permanance of gained endless belt in table 3, have been listed.

Embodiment 13

Except selecting kneading condition and condition of moulding to make it not form the island structure, use the method identical to obtain to have the endless belt of non-island structure with embodiment 6-12, wherein PBT and PC evenly disperse each other.Dispersed texture, machinery and electric property and the permanance of gained endless belt in table 3, have been listed.

Table 3

			Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 3
												Form	PBT (weight portion)		60	77	?60	?60	?60	?60	?60	?60	?60
PC (weight portion)		26	9	?29	?25	?26	?26	?26	?26	?26
											Catalyzer (in total resin weight)		The content of titanium (ppm)	60	60	?60	?60	?60	?60	?60	?60	?0
The content of magnesium (ppm)	25	25	?25	?25	?25	?25	?25	?25	?0
										Carbon black (weight portion)			14	14	?11	?16	?0	?14	?14	?14	?14
PEPQ (weight portion)		1	0.3	?1	?0.3	?1	?1	?1	?0.3													?1
										The kneading condition	Temperature (℃)		260	240	?240	?240	?240	?240	?240	?250	?240
Screw speed (rpm)		150	150	?150	?150	?150	?150	?150	?150													?150
											Output (kg/hr)		15	15	?15	?15	?15	?20	?20	?20	?15
Hold-up time (min)		About 2	About 2	About 2	About 2	About 2	About 2	About 2	About 2													About 2
											Condition of moulding	Molding temperature (℃)		240	240	?240	?240	?240	?240	?240	?260		?240
Hold-up time (min)		About 12	About 13	About 12	About 12	About 13	About 16	About 10	About 10	About 10
												Flex life			20,000	35,000	?25,000	?15,000	?25,000	?10,000	?40,000	?90,000	?3,400
Tensile modulus (MPa)	5℃		2700	2600	?2800	?2600	?2300	?2700	?2700	?2400	?2800
												40℃		2300	2200	?2500	?2300	?2000	?2300	?2300	?2100	?2600
	60℃		1300	1000	?1100	?1400	?1000	?1300	?1300	?300	?1300
												The melting peak temperature between the DSC for the first time and for the second time poor (℃)			10	5	?6	?4	?15	?8	?10	?35	?2
Thickness (μ m)			140±10	140±10	?140±10	?140±10	?140±10	?200±18	?100±5	?140±10	?140±10
												Surface resistivity (Ω)	Minimum		1×10 10	1×10 10	?1×10 12	?1×10 7	?1?×10 15	?2×10 8	?2×10 10	?1×10 9	?2×10 9
Maximum		4×10 10	6×10 10	?8×10 12	?3×10 7	?3×10 15	?8×10 8	?8×10 10	?8×10 9	?8×10 9
											Specific insulation (Ω cm)		Minimum		1×10 9	2×10 10	?1×10 12	?1×10 7	?1×10 15	?1×10 9	?1×10 10	?1×10 10	?1×10 10
Maximum		8×10 9	9×10 10	?8×10 12	?3×10 7	?3?×10 15	?8×10 9	?8×10 10	?8×10 10	?8×10 10
												The permanance of band	Produce the crack *		200,000	200,000	?200,000	?200,000	?200,000	?200,000	?200,000	?200,000	Produce after finishing 60,000 copies
Because of stretching image fault **		200,000	200,000	?200,000	?200,000	?200,000	?200,000	?200,000	Find after finishing 60,000 copies	Find after finishing 60,000 copies
											Dispersed texture			Island structure	Island structure	Island structure	Island structure	Island structure	Island structure	Island structure	Non-island structure	Island structure
Overall assessment			Good	Good	Good	Good	Good	Good	Good	Can accept													Difference

^*In the quantity of being with output copy under the situation that does not produce the crack

^*The quantity that does not have output copy under the situation of distortion at image

As seen in from table 3, all endless belts of the present invention have high tensile modulus in wider temperature range, excellent permanance and gratifying anti-crawl agentdefiection performance.On the contrary, the band in the comparative example 3 for preparing under not having the polymerization catalyst situation has not enough anti-crawl agentdefiection performance, and produces crack and image fault after finishing 60,000 copies.In embodiment 13, though used polymerization catalyst, kneading and molding temperature are provided with height, and this has just caused the formation of non-island structure.Therefore, the band among the embodiment 13 shows very big difference between measuring for the first time under the DSC melt temperature and measuring for the second time.Its tensile modulus is little down at high temperature (60 ℃) for the result, and produces image fault owing to the stretching of band after producing 60,000 copies.

The invention provides a kind of mechanograph with high tensile modulus, these goods have excellent anti-crawl agentdefiection performance, chemical-resistance and molding dimensional stability, and do not have physical deterioration owing to react during melting mixing.Mechanograph of the present invention is particularly suited for as the endless belt.

Describe in detail with reference to specific embodiment in this present invention, to those skilled in the art, under the situation that does not deviate from purport of the present invention and scope, it is carried out various changes and modifications is conspicuous.

The application is based on the Japanese patent application No.Hei.11-372335 of application on Dec 28th, 1999, No.Hei.11-372336, No.Hei.11-372338, with the Japanese patent application No.2000-35535 and the No.2000-35536 of application on February 14th, 2000, their all the elements are all incorporated the present invention into as a reference.

Claims (24)

1. mechanograph, comprise by in heating, having crystalline resins at least a in hydroxyl, carboxyl and the ester bond, has amorphous resin at least a in hydroxyl, carboxyl and the ester bond, mixed with polymerization catalyst and to be prepared resin combination, and this resin combination of molding and the mechanograph that obtains.

2. mechanograph according to claim 1, its differential scanning calorimetry curve representation, the difference between the peak temperature of the melting peak that heats up for the second time in the back of the gentle cooling in the peak of the melting peak that heats up for the first time is 30 ℃ or littler.

3. mechanograph according to claim 1, wherein these goods have island structure.

4. mechanograph according to claim 1, wherein these goods contain the chemical bond that forms between the strand of the strand of described crystalline resins and described amorphous resin.

5. as mechanograph as described in the claim 4, wherein the total amount of every mole of corresponding described crystalline resins of described chemical bond and described amorphous resin is 300,000g or still less.

6. mechanograph according to claim 1, the weight ratio of wherein said crystalline resins and described amorphous resin is 1/99 to 99/1, and in described crystalline resins and described amorphous resin total amount, described polymerization catalyst contains 1-10, the metal of 000ppm.

7. mechanograph according to claim 1, the weight-average molecular weight (Mw that the blending ratio of wherein said crystalline resins (X weight portion), described crystalline resins transform according to polystyrene ₁), the weight-average molecular weight (Mw that transforms according to polystyrene of the blending ratio (Y weight portion) of described amorphous resin, described amorphous resin ₂) and the weight-average molecular weight (Mw that transforms according to polystyrene by the described resin combination that in heating, crystalline resins, amorphous resin and polymerization catalyst is mixed with ₃) between should satisfy following relational expression:

Mw ₃≥[X/(X＋Y)]×Mw ₁＋[Y/(X＋Y)]×Mw ₂

8. mechanograph according to claim 1, wherein the weight-average molecular weight that transforms according to polystyrene is 130,000 or more.

9. mechanograph according to claim 1, wherein said polymerization catalyst contains titanium.

10. mechanograph according to claim 1, wherein said polymerization catalyst contains titanium and at least a element that is selected from alkaline metal, earth alkali metal and zinc.

11. as mechanograph as described in the claim 10, wherein said at least a element is a magnesium.

12. mechanograph according to claim 1, wherein said crystalline resins is a polyalkylene terephthalates.

13. as mechanograph as described in the claim 12, wherein said polyalkylene terephthalates is a polybutylene terephthalate.

14. mechanograph according to claim 1, wherein said amorphous resin is a polycarbonate.

15. mechanograph according to claim 1, wherein these goods contain the carbon black of 3-30% weight as conductive filler.

16. an endless belt comprises as each described mechanograph in the claim 1 to 15.

17. as endless belt as described in the claim 16, wherein this band is 5000 or more according to the folding resistance that JIS P-8115 measures along the circumferential direction, tensile modulus along the circumferential direction is 1500 to 5000MPa, and is 30% or more along the breaking elongation of circumference and width both direction.

18. as endless belt as described in the claim 16, the tensile modulus under its 40 ℃ is 60% under 5 ℃ or higher, the tensile modulus under its 60 ℃ is 20% under 5 ℃ or higher.

19. as endless belt as described in the claim 16, wherein this band has 1 * 10 ¹-1 * 10 ¹⁶The surface resistivity of Ω or 1 * 10 ¹-1 * 10 ¹⁶Ω cm specific insulation, the maximal value of wherein said surface resistivity or specific insulation are not more than 100 times of minimum value.

20. as endless belt as described in the claim 16, wherein this band has the average thickness of 70-300 μ m.

21. as endless belt as described in the claim 16, wherein this is with and is the seamless band.

22. as endless belt as described in the claim 16, wherein this is with the seamless band for melt extruding and cool off from ring-like mouthful of mould.

23. be used for the endless belt of imaging device, comprise the endless belt in the claim 16.

24. an imaging device comprises the endless belt in the claim 23.

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